Solid state NMR spectroscopy has been used in this work to investigate crystallinity of cellulose in spruce wood before and after kraft pulping and TCF bleaching. Effects of refining of the spruce kraft pulp in water and in weak alkali have been studied by determination of the crystallinity of isolated fines and corresponding bulk fibres in order to find out whether the crystallinity in the fibre surface material and inside the fibre wall differ from each other. Also the possible effect of enzymatic endo-1,4-β-galactanase treatment on the crystallinity of some refined pulps has been investigated. It was found that the Iα crystalline form of cellulose predominates over the Iβ form in native spruce and vice versa in all the pulps studied. In pulping part of the cellulose Iα is converted to the more stable Iβ form mainly by heat. Any measurable changes in the degree of crystallinity or in the relative proportions of different crystalline forms of cellulose could not be seen in pulps after refining, TCF-bleaching or galactanase treatment. However, the degree of crystallinity was found to be considerably lower in the fines compared to the corresponding bulk fibres. Therefore it is suggested that the cellulose crystallinity is lower or the size of crystallites smaller on the fibre surface than inside the fibre wall. Slightly higher contents of lignin and hemicelluloses, mainly xylan and mannan, were also found in the fines compared to the bulk fibres.
Liitiä, T., Maunu, S-L., & Hortling, B. (2000). Solid state NMR studies in cellulose crystallinity in fines and bulk fibres separated from refined kraft pulp. Holzforschung, 54(6), 618-624. https://doi.org/10.1515/HF.2000.104